c dfrancesco sansone, alessandro casnati, mario marianic dfrancesco sansone, alessandro casnati, d *...
TRANSCRIPT
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Electronic Supplementary Information
2,9-Dicarbonyl-1,10-phenanthroline derivatives with unprecedented Am(III)/Eu(III) selectivity under highly acidic conditions
Michele Galletta,a Stefano Scaravaggi,a Elena Macerata,a Antonino Famulari,b Andrea Mele,b Walter
Panzeri,c Francesco Sansone,d Alessandro Casnati,d * Mario Mariania*
aDepartment of Energy, Politecnico di Milano, Via Lambruschini 4, I-20156 Milano, Italy bDepartment of Chemistry, Materials and Materials Engineering, Politecnico di Milano, Piazza L. da Vinci, 32 I-20133 Milano, Italy cCNR-Istituto di Chimica del Riconoscimento Molecolare, via L. Mancinelli 7, I-20131 Milano, Italy dDepartment of Chemistry, University of Parma, Parco Area delle Scienze 17/a, I-43124 Parma, Italy
Index
Table SI1 Distribution coefficients of Am(III) and Eu(III) and separation factors Am/Eu as a function of initial nitric acid. Page S2
Figure SI1 ESI-MS of ligand 4 before the contact with 3.82 M HNO3. Page S3
Figure SI2 ESI-MS of ligand 4 after the contact with 3.82 M HNO3. Page S4
Figure SI3 ESI-MS of solution containing ligand 4 and Eu nitrate in methanol. Page S5
Figure SI4 Optimized structure of the ligand 9 obtained by DFT calculations. Page S6
Table SI2 Selection of Eu to O/N atom distances in the [Eu(9)(NO3-)2]+ complex
as measured in the DFT minimised structure. Page S6
Table SI3 Selection of Eu to O/N atom distances in the [Eu(9)2(NO3-)]2+ complex
as measured in the DFT minimised structure. Page S6
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013
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Table SI1: Distribution coefficients of Am(III) and Eu(III) and separation factors Am/Eu as a function of initial nitric acid. Aqueous phase: [HNO3] = 0.001 to 3.82 M; Organic phase: [L] = 0.01 or 0.02 M + [Br-cosan] = 0.02 or 0.01 M in NPHE; (mixing time: 60 min, temperature: 22 ± 2°C).
Ligand
AQUEOUS PHASE ORGANIC PHASE [HNO3] 1-
Octanol Kerosene NPHE [L] / [Br-Cosan] = 0.5 in NPHE
[L] / [Br-Cosan] = 1 in NPHE
[L] / [Br-Cosan] = 2 in NPHE
1
0.01 n.a. 0.017 n.a. > 1000 515.4
D-Am 0.1 n.a. n.a. n.a. 1.45 8.16 1 0.0005 n.a. 0.0073 0.0546 0.291
3.82 0.0031 0.0265 0.0562 0.0188 0.164 0.01 n.a. 0.0157 n.a. > 1000 62.95
D-Eu 0.1 n.a. n.a. n.a. 0.253 0.234 1 0.0001 n.a. 0.001 0.0138 0.007
3.82 0.0018 0.0087 0.0066 0.0022 0.013 0.01 n.a. 1.08 n.a. n.a. 8.19
SF Am/Eu 0.1 n.a. n.a. n.a. 5.74 34.8 1 3.5 n.a. 7.62 3.96 41.7
3.82 1.68 3.04 8.56 8.71 12.5
2
0.001 n.a. 9.66 2.15 0.0430
D-Am 0.01 n.a. 11.9 0.827 0.1 n.a. 1.14 0.0462 1 0.0821 0.0085 0.0013
3.82 0.0158 n.a. 0.0027 0.001 n.a. 0.55 0.124 0.0086
D-Eu 0.01 n.a. 0.962 0.0815 0.1 n.a. 0.0759 0.0036 1 0.0769 0.0023 0.0002
3.82 0.0033 n.a. 0.0004 0.001 n.a. 17.7 17.3 5.00
SF Am/Eu 0.01 n.a. 12.3 10.2 0.1 n.a. 15.0 12.8 1 1.07 3.69 8.86
3.82 4.76 n.a. 6.31
3
0.01 0.0634 D-Am 0.1 0.0089
3.82 0.0131 0.01 0.01
D-Eu 0.1 0.0016 3.82 0.0117 0.01 6.31
SF Am/Eu 0.1 5.89 3.82 1.12
4
0.001 n.a. n.a. n.a. n.a 0.0022
D-Am 0.01 n.a. 0.1236 0.001 1.53 0.0036 0.1 n.a. n.a. n.a. 0.0568 n.a. 1 n.a. n.a. n.a. 0.0035 n.a.
3.82 0.0019 n.a. n.a. 0.0055 0.0687 0.001 n.a. n.a. n.a. n.a. 0.0018
D-Eu 0.01 n.a. 0.122 0.0007 0.623 0.0046 0.1 n.a. n.a. n.a. 0.0221 n.a. 1 n.a. n.a. n.a. 0.0015 n.a.
3.82 0.0019 n.a. n.a. 0.0011 0.0051 0.001 n.a. n.a. n.a. n.a. 1.22
SF Am/Eu 0.01 n.a. 1.01 1.43 2.45 0.79 0.1 n.a. n.a. n.a. 2.57 n.a. 1 n.a. n.a. n.a. 2.31 n.a.
3.82 1 n.a. n.a. 4.87 13.4
Note: blank cells = non tested; n.a. = data not available
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013
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Figu
re S
I1: E
SI-M
S of
liga
nd 4
bef
ore
the
cont
act w
ith H
NO
3 3.8
2 M
[4*N
a]+
[4*H
]+
[NPH
E*N
a]+
[NPH
E 2*N
a]+
[4*C
s]+
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013
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[NPH
E*N
a]+
[NPH
E 2*N
a]+
[1*N
a]+
[1*N
a-O
+S]+
[1*H
]+ [1
*Cs]
+
Figu
re S
I2: E
SI-M
S of
liga
nd 4
aft
er th
e co
ntac
t with
HN
O3 3
.82
M
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013
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Figu
re S
I3: E
SI-M
S of
a so
lutio
n co
ntai
ning
liga
nd 4
and
Eu
nitr
ate
in m
etha
nol i
n th
e ra
tio 1
:10
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013
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Figure SI4. A view of the optimized structure of the ligand 9 obtained by DFT calculations.
Table SI2: Selection of Eu to O/N atom distances in the [Eu(9)(NO3-)2]+ complex as measured in the DFT
minimised structure.
[Eu(1)(NO3-)2]+
Bond Length (Å) M-N1,2 2.62 M-O1,2 2.46 M-O5,5’ 2.56 M-O6,6’ 2.47
Table SI3: Selection of Eu to O/N atom distances in the [Eu(9)2(NO3-)]2+ complex as measured in the DFT
minimised structure.
[Eu(1)2(NO3
-)]2+ Bond Length (Å)
M-N1,2 2.68 M-O1,2 2.55 M-O4 2.41
M-O5,6 2.52 Non-bonded (Å)
M-N4 3.39 M-N3 4.04 M-O3 4.99
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2013